Copper containing disazo dyestuffs



Patented Mar. 3.0, 1948 2,438,754 COPPER CONTAINING DISAZO DYESTUFFS Adolf Krebser, Riehen, near Basel, and Werner Bossard, Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel, Switzerland N Drawing.

Application March 1, 1943, Serial No. 477,630. In Switzerland April 28, 1942 11 Claims. 1

It has been found that valuable new coppercontaimng disazo dyestuffs are obtained by coupling a diazotised amino sulfonic acid of the benzene or naphthalene series, which contains, in o-position to the amino group, a hydroxy group or a. substituent convertible into a hydroxy group by coppering, with a 1:3-dihydroxy-benzene, then causing a diazonium compound which is free from sulfonic acid groups to react with the said monoazo dyestufi' and after-treating the so-obtained disazo dyestufi with copper-yielding agents, with the condition that at least one of the diazo components is substituted by a phenyl nucleus bound by a non-basic bridge. The same copper-containing disazo 'dyestuff is obtained by coppering the monoazo dyestuff obtained from with copper-yielding agents.

As non-basic bridges between two phenyl nuclei of the diazo components there may be enumerated for instance: SO2--, SO2NC2H5-,

-CO, and the like. From the above definition or cresyl ester, 2-, 3- :or l-amino-l-hydroxyben the following three types of dyestrufi's may be derived:

(a) The first diazonium component is mononuclear, while the second diazonium body'con-' tains two aryl nuclei linked together by a nonmethoxy- For the dyestuifs of the type (a): Z-amino- 1-hydroxy-, -methoxyor -benzyloxybenz ene,- 4-sulfonic acid, 4- or 6-methy1-2-amino-1-hydroxy-- or ethoxybenzene sulfonic acid, 4- or (i-chloro-Z-amino-l-hydroxypr -methoxybenzene sulfonic acid, 4- or 6-nitro-2-amino-1-hydroxyor -methoxybenzene sulfonic acid, 1-amino-2-hydroxynaphthalene-4-su1fonic acid, 6 nitro-2-amino-l-hydroxynaphthalene 4 sulfonic acid.

For the dyestuffs of the type (b) and- (c): 3-amino-4-hydroXy-, -methoxyor -chloro-1:1'- diphenylsulfone-5- or -3'-sulfom'c acid, 3-amino- 4-hydroxy- 0r methoxybenzene-l-sulfonic acid ethy1ani1ide-3'- or -4'-'sulfonic acid, 3-ainino- 4-hydroxyor -methoxybenzene-1-sulfonic acid phenylester-3-sulfonic acid, 3-amino-4-hy droxy-1:1'-diphenylether sulfonic acid.

The second diazonium compound can be obtained from the following amines:

For the dyestuffs of the type (a) and (c); 4- or G-methylor -methoxyor -chloro- 3-amino-1:1'-dipheny1sulfone, 4- 301' 6-methyl-, -methoxyor -ch1oro-3-aminobenzene-l-sulfonic, acid ethylanilide, 4- or 6-methy1-, -methoxyor -chloro-3-aminobenzene-l-sulfonic acid phenylzene-benzene, -tolueneor -chlorobenzene sultonic acid ester, 2- or 4-amino-1:1'-diphenyl ether, its alkylor halogen substitution products;

For the dyestuffs of the type (b): 2-methyl or -chloro-4- or -5-nitro-1aminobenzene. i

The dyestuffs obtained according to the present invention possess excellent drawing properties,

when applied to silk from a neutral dyebath.

' Beside good washingand water-fastness properties they are especially distinguished by an excellent light-fastness.

The present invention is illustrated, but not limited, by the following examples, the parts being by weight, unless otherwise stated.

Example 1 32.9 parts of '3-amino-4-hydroxy-l:1-diphenyl-sulfone-3'-sulfonic acid are dissolved 1:3-dihydroxybenzene in 50 parts of water and 14 parts of sodium hydroxide. After 4 hours the monoazo dyestufi thus formed is precipitated by means of hydrochloric acid, filtered off and it 6 P s Of s um b n te in Water. then coupled in an acetic acid suspension with the intermixed with 6.9 parts of sodium nitrite and diazotised by allowing to run into 23 parts of hydrochloric acid at 5 C. The diazo compound thus partly precipitated is combined with' 11 diazo body from 19.6 parts of 2-methyl-2-amino- 1:1'-diphenyl ether. disazo dyestuff into the copper complex compound it is treated at 90 C. with 25 parts of crystallised parts of -d o y e in a caustic alkacopper sulfate, then precipitated and converted line medium. For the conversion of the monoazo dyestufi, which has been separated out in an acid medium, into the copper complex compound it is stirred at 90 C. for 30 minutes with 25 parts of crystallised copper sulfate, then salted out,

into the sodium salt in the usual manner. It dyes wool and silk in vivid brown shades of good light and wetting fastness.

Example 5 20.3 parts of 2-amino-1-methoxybenzene-4- sulfonic acid are diazctised in the usual manner,

coupled in a soda alkaline solution with 11 parts r of 1:3-dihydroxybenzene and separated out by acidifying the" solution. For'the conversion of of sodiui'ii "chloride; Tli'is dyestatt ayes animal fibres in yellowish-brown shades of excellent lightand washlng-fastness.

'When, on the other hand, the coupling of the coppered monoazio ti i om'fi l i f ffi tallised copper sulfate. vThe copper-containing .o hydroxy azodyestuff is finally coupled with T the iam-compound from 24.7 parts of 4-methylthe diazonium compound from 16.8 parts 0 5-nitro-2-amino- 1 -methdxybenaefi with diazotised 4-methyl-3 amino diphenylsulfone, a dyestufi of equally good f'a'stiiiessprep erties is obtained which gives da rk brown shades on fibres.

aiiiilib l hydroxybenzen'ei sulfnic acid is com a (iill'stic alkali'ffe solution of 1 1 pal-ts dinyurexyben'zene; When the eeu pimg has completed; the monet ze dyestue ispie- Wait er $12280 Cw, treated with 25 arts 6f 'crystailised copper s lfate and the whole is maimtamed-ici- 1 nonfat; 90* o. The copper-containin? dyestu ft thus preci itated is filtered gir and c 'erte-u into the sodium salt by meansofknow'n' veryseed fasti'iess properties.

, Example 3 11 parts 'of 1:3-amyaroxybentene are combined-at 0 C, thepresence of 1 4' parts ofsod'iiifii hydroxide, with the'diazo compound obtaifie'dfrom 372 parts of. aminol-hydroxybeniene l-sulfonic' acid ethylan-ilide-4'-sulfonic acid; 7 The monoa-zo dyestufi isolated imangac'id medium and again dissolvedin water is treated or--1--hour with: 2-5-parts of'c'rysta-l'lised copper Sulfate. The monoazd dyestu'if thus coppered is tl feir'separa't'ed "dissolved water and fcoifipled M ptlun'dTrofii' 163' parts of 5=fiitro-2-aiiiin methoxybenzene. The dyestuff, Worked u ds'dribed in nixamp ez, dyes wool ar'i'd silk in shades ef izte-iient fa's'tiiss proper tee w y 7 V methods ere-"emulsifie et- 6" dwith ii paifts of 75 good tastness properties;

the mono'azo dyestuff into the copper complex compound the same is dissolved in water and --boiled for several hours in the presence of 20' parts of sodium acetate with 25 parts of crys- ;3garriino lgl diphenylsulfone in an acetic acid suspension thus giving the disazo dyestufi. The iormationfof tlie dyestufi can be accelerated by sodium; carbonate solution. The dyestuff soobtained dyes silk in reddish-brown shades of good fastness proper-ties. V V r Example 6 The monoazo dyestufi obtainable accordingto Example 1 from 32.9 parts of 3-amino-4-hydroxy-l' z l'-diphenylsulfone-3'-su1fonic acid and 40 1 1 parts of rcsorcinol is coppered, as mentioned" in thesaid Example 1, by means of 25 parts of crystallised copper sulfate and coupled in i an acetic acid solution with the diazo compound from: 26 .1 parts er the p-toluene sulfonic acid ester ofthe e-aminophenol. The completely formed dyestufl' is precipitated by means of sodium chloride. yellgwish-brownshades.

When, instead of the mono'azodyestufi obmfihodvs i dyes" Sin; in fdep i shqaldis 6f tained according to Ex'amplel, there is usedtha-t obtainable according to Example 2 from 1819 parts of diazotised 2-amino-l-hydroxybenzene- 4-sulfonic acid and 11 parts of 1:3-dihydroxybenzene and worked up as indicatedabove; a dyestufi is obtained which dyes animal fibres in 34.5 parts 'of, '3'-amino-4-hydroxybenzene-1- s'ulfoiiic' acid phenyl-ester-3" -sulfonic acid are diazotised indirectly and coupled at ,0 C; inthe dyestu'ff is'ol'ated'by acidification is converted at 80. C. into'the copper complexcompound by adding 25 parts of crystallised copper sulfate and coupled with the diazo compound from 24.7 parts .dyestuif dyes wool and silk in brown shades of In order to convert the gfafdually' neutralising the solution with dilute- It dyes silk and Wool in fast resence of, exceedin causticsoda lye with 11, in 'ait'ac'etic acfd'suspeiision vote-mediate 'com- Parts l3'dlhydmxybenzene- The In the following table rurther examples illustrating the present invention are enumerated:

arylam'ine of the benzene series, with the condition that. at least one of the radicals A and C is dyeing of the Example 1st diazo compound middle component 2nd diazo: compound 1 copper complex compound 4"-aminophenyl'-4methylbenzene sulbrown.

6methyl-2-aminoI-hydroxybenzene-4-sulionic acid.

3amino-iehydroxybenzene-l-sulfonic acidmethyl-anilide'-4"-sulionic acid.

1:3-dihydroxybenzene. -do

fomc acid ester.

4methyl-3-amino-1:1-diphenyl-sulione yellowish-brown.

3aniino hhydroxy-1:1'-diphenylsulfone- 4-amyl-2-amino-1:1'-diphenyl ether Do. 3-sulfonic acid.

i-niigo- 1;amigo-z-hydroxynaphthalene6- 6-methyl-3-amino-1:1-diphenyl-sulfone violet brown.

su omc acl i-chloro-tliamino-1-hydroztybenzene-fid-methoxy-S-amino-l:l-dipheny1sulfone. brown.

omc aci 2-aminc1methoxy-benzene-4-sulionic acid. 6-chloro-3-amino-1:1'-diphenylsulfonereddish-brown. 3-aminoA-hydroxybenzene-l-sulfonic aoid- 2'-methyl-2-am1no-l:l'-d1phenyl other" brown.

ethylanllide-3-sulfonic acid. (i-methyl-Z-aminodhydroxybenzene4- 'B-rcsorcylic acid 3-amino-6-phenylamino-1:1-diphenylred-brown. sulfonic acid. sulfone. 3amino4-hydroxybenzene-l-sulfonic acid- 1:3-dihydroxy-benlo Do.

ethyl-anilide-4-sulfonic acid. zcne. 2amino-1hydroxybenzeneAsulfrinioacid. do 3-aminobenzophenone brown. d-amino-d-hydlroxyd:ldiphenyl'sulfone-W- .-do- 4-methoxy-3-amino-1:1'-dipheny1su1fone nigger-brown.

sulfonieaci do 2-methyl-fi-nitro-l-aminobenzene yellowish-brown.

2-chloro5-11itr0-1-an1inobenzene olive-brown. L ydroxybenzeneA-sulfonicaci 2:4-dichloro-2-amino-1:1-dipl1enylether reddish-brown. v do 3-aminobenzene-sulionic acid-2 cresyl- Do.

ester.

23 2-amino1methoxybenzeneA-sulfonic acid .-do-. i-chlorobenzene-sulfonic acid-4-amino- Do.

' phenyl ester. 24 2-amino-1hydroxybenzene--sulfonic acicL. fl-resorcylic acid 6mfizlfiyl-tyaimino-benzene-sulonic acid Do.

e y am 1 e. 25 .do 1:3-dihydroxyben- 4-methylbenzene-sulionicacid-2-aminobrown.

zene. phenyl ester. 26 2-ami110leth0xy-benzene-4-sulf0nicacid d0 3-aminobenzoyl-ethylanilide reddish-brown. 27 1amgm-2hydroxynaphthaleneA-sulfonic do 2-amino-2-methyl-l:1-diphenylcther grey.

aci 28 3amino4-hydroxy-I:Y-diphenylsulfone-fido 4-methyl-3-amino-1:1diphenyl-sulione brown.

sulfonicacid. 7 29 "do .d0 4-amin0benz0phenono Do.

What we claim is:

1. A process for the manufacture of coppercontaining disazo dyestuffs of the general formula A-N=N-B--N=NC wherein A stands for a sulfonated aryl radical of the benzene series containing in o-position to the azo group a group capable of being coppered, B stands for a radical of a 1:3-dihydroxybenzene and C stands for an unsulfonated aryl radical of the benzene series, which comprises diazotising an amin'oarylsulfonic acid of the benzene series containing in o-position to the amino group a group capable of being coppered, coupling the diazo compound with a 1 :3-dihydroxybenzene and coupling the monoazo dyestuif with a diazotised unsulfonated arylamine of the benzene series, with the condition that at least one of the radicals A and C is linked to a benzene radical by means of a member selected from the group con; sisting of SO2,

s O21| Talky1 SO2O, O-, and CO--, and converting the dyestuff into its copper complex compound.

2. A process for the manufacture of coppercontaining disazo dyestuffs of the general formula wherein A stands for a sulfonated aryl radical of the benzene series containing in o-position to the azo group a group capable of being'coppered, B stands for a radical of a 1:3-dihydroxybenzene and C stands for an unsulfonated aryl radical of the benzene series, which comprises diazotising an aminoarylsulfonic acid of the benzene series containing in o-position to the amino group a group capable of being coppered, coupling the diazo compound with a 1:3-dihydroxybenzene, converting the monoazo dyestuff into its copper complex compound and coupling the coppered monoazo dyestuff with a diazotised unsulfonated linked to a benzene radical by means of a. member selected from the group consisting of S02-,

3. A process for the manufacture of copperoontaining diazo dyestuffs of the genera1 formula.

SOzH

SO2-O, -O-, and -CO, While Y represents a group capable of being coppered, which comprises coupling a 1:3-dihydroxybenzene with a diazotised amine of the formula SOsH wherein X and Y have the above 'mentioned Si nifications, converting" the monoazo dyestufi into its copper complex compound and coupling the monoazo dyestufi with a diazotised unsulfonated arylamine of the benzene series.

4. A process for the manufacture of copper- 7' containing disazo dyestuffs of the formula wherein B stands for a radical of a,1:3-dihydroxybenzene and stands for an unsulfonatedaryl radical of the benzene series, which comprises coupling a 1:3-dihydroxybenzene with a diazotised 3-amino-4-hydroxy-1: l'-diphenylsu1- tone sulfonic acid of the formula SOaH converting the monoazo dyestuff into its copper complex compound and coupling the monoazo dyestufi with a diazotised unsulfonated arylamine of the benzene series.

5. A process for the manufacture of a copperwhich comprises coupling lz3-dihydroxybenzene with diazotised 3 amino 4 hydroxy 1:1-diphenylsulfone-3'-sulfonic acid, converting the dyestufi into its copper complex compound and coupling the monoazo dyestuif with diazotised 3- amino-4-methy1- 1: 1'-dipheny1sulfone.

- '6. A process for'the manufacture of a coppercontaining diazo dyestufi of the formula OH OH OGHa;

sonar which comprises coupling 1:3-dihydroxybenzene with diazotised 3 amino 4 hydroxy-1:1'-diphenylsulfone-3'-sulfonic acid, converting the dyestufl into its copper complex compound and coupling the monoazo' dyestuff with diazotised 2- amino-1-methoxy-5-nitrobenzene.

7. A process for the manufacture of a coppercontaining disazo dyestufi. of the formula on on Q I v is:

V Gobf-Ocm which comprises coupling 1: 3 -dihydroxybenzene with diazotised 2-amino-l-hydroxybenzene l-sul fonic acid, converting the monoazo dyestufi into its copper complex compound and coupling the monoazo dyestuff with diazotisedfl-amino-l hydroxy-benzene-p-t0luenesulfonic acid ester.

8. The copper-containing dyestuffs of the gen- 7 eral formula wherein A stands for a sulfonated aryl radical of the benzene series containing in o-position to the azo group a group capable of being coppered, B stands for a radical of a 1:3-dihydroxybenzene and C stands for an unsulfonated aryl radical of the benzene series and wherein at least one of the groups A and C is linked to a benzene radical by means of a member selected from the group consisting of -SOz,'

'SO2O-, -O-,'and -CO, being dark powders dissolving in water with brownish color, in concentrated sulfuric acid with orange to red color and dyeing fibres in brown shades of excellent fastness if coppered.

9. 'Ifhe copper-containingdyestufi oithe formula v v 7 V I OH OH OH CH3 SOsH being a dark powder dissolving in water with olive-brown color, in concentrated sulfuric acid with red color and dyeing fibres in dark brown shades of very good fastness to light and washing if coppered.

10 11. The copper-containing dyestuff of the formula being a dark powder dissolving in water with yellowish brown color, in concentrated sulfuric acid with orange color and dyeing fibres in reddish brown shades of very good fastness if coppered.

ADOLF KREBSER. WERNER BOSSARD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,117,731 Kollmann May 17, 1938 2,135,433 Delfs et al Nov. 1, 1938 2,160,448 Wehrli May 30, 1939 2,257,165 Fellmer Sept. 30, 1941 

